Resinous compositions



I especially valuable for certain purposes.

Patented F ob. 21, 1950 RESINOUS COMPOSITIONS Ludwig H. Dimpfl, Berkeley, Calif., assignor to California Research Corporation, SanFrancisco, Calif., a corporation of Delaware No Drawing. Application March 19, 1946, Serial No. 655,598

9 Claims. (Cl. 260-45.!)

This invention relates to new thermosetting compositions and methods whereby they may be prepared.

More particularly the invention is concerned with the production of compositions that may be cured in a few minutes without a catalyst at temperatures as low as 70-90 C. The chemical reaction whereby these compositions are formed is such that negligible amounts of water or volatile products'are liberated during curing. This lends certain advantages for the composition is relatively free from surface crazing, blow-holes, splitting or shrinking during the curing process. The absence of shrinking permits molding to close tolerances.

The polymers comprisingthis invention may be formed using widely varying proportions of two types of thermoplastic polymers. Type I is the linear condensation polymer of a cyclohexadiene dicarboxylic acid, and Type II is the linear polymer containing an average of more than two activated olefin bonds in the molecule. I

It has been discovered that such polymers possess certain properties which render them For example, they possess high water resistance, are insoluble in most organic solvents, light in color, hard, tough and may be varied in mechanical properties in accordance with specific requirements.

The polymers comprising this invention have properties that make them especially useful as components of surface coating materials, ad hesives, wood laminates, molded plastics, and the like.

An important feature of the invention is the correlation between the average number of cyclohexadiene nuclei in the Type I polymer molecule with the average number of activated olefin groups in Type II polymer molecule to obtain relatively rapid thermosetting rates. It has been found that where "A" represents the average number of cyclohexadiene dicarboxylic acid residues per molecule in Type I polymer and B represents the average number of activated olefin bonds per molecule in Type II polymer the mathematical product of (A"-2) and (B-2) should be at least about to yield measurably accelerated thermosetting rates. It is preferred that the values of "A and B" be such that the foregoing mathematical product is greater than about in which case relatively rapid thermosetting rates are obtained at temperatures of 90-150 C.

The cyclohexadiene dicarboxylic acids from which Type I polymers may be prepared exist in v 2 a number of related isomeric forms. The system of nomenclature utilized here for identifying these acids follows the standard system of numbering carbon atoms of the cyclohexadiene ring,

'as' illustrated by the following, wherein the ring carbons are numbered beginning with the first carboxyl group and A indicates the positions of (Full formula) (Abbreviated formula) A3,5 cyclohexadien'e dicarboxylic acid 1,2

TYPE I THERMOPLASTIC POLYMERS In order to carry out this invention one prepares a member of a first type of long chain polymers formed in the reaction between cyclohexadiene dicarboxylic acid-1,2 and a dibasic alcohol or diamine such as ethylene glycol or ethylene diamine. Such thermoplastic polymers react with one another to form long chains which may be illustrated as follows:

' carboxylic acids is the 133,5 cyclohexadiene dicarboxylic acid-1,2.

TYPE 11 THERMOPLASTIC POLYMERS Additionally, in order to carry out this invention one prepares a second type of linear polymer containing at least two activated olefin bonds per molecule, such as the linear condensation polymeans mer of maleic acid. and a diamine or dihydricalcohol such as ethylene diamine or ethylene glycol. Such linear polymers comprise long chains which may be illustrated as follows:

Lil-lions].

where Y is a residue of a bifunctional alcohol or amine, i. e.,-one.containing two hydroxy orwtwo amine groups or one-amine and one hydroxy where X and Y are dibasic alcohol or diamine residues as described above.

A member of each :or the first and second types of to produce the thermosetting of water accumulates in the trap. The heating is discontinued and the product is transferred to a flask equipped for stirring under vacuum. The

solvent is distilled oil at atmospheric pressure until the liquid temperature reaches 140 C. Vacuum is then applied and-stirring and heating continued until no more solvent appears to distill oil at a liquid temperature of 150 C. and 10 mm. of mercury pressure. The melt is then transferred toa container and allowed to cool. A soft, amber solid is obtained. The value of (A-2) of this product is 5.5.

PREPARATION OF POLYLlERS-TYPE li'ammple 2.A polymeric ester comprising the reaction product of ethylene glycol and maleic anhydride is prepared by adding 98 grams of maleic anhydride and 62 grams of ethylene glycol in a 500 m1; flask equipped for stirring under vacuum. The temperature is raised to 180 C. in minutes, held at 180 C. and atmospheric pressurefor 1 hour and minutes, and finally held at 180 C.

and 30-50 mm. of mercury for 30 minutes or until the near-gel stage is reached. The melt is transferred to a flask and gives a transparent waterwhite plastic solid when cool. The value of (3-2) "of this product is 5.0.

The thermoplastic polymers, pe I and Type 11, 'may be used in the form of lumps, powder, granules, solution or a state of fusion. They may added'tcgether in amounts such that the final composition contains Type I polymer in the range of 5 to 95 percent and contains Type II polymer in the range of 5 to 95 percent whereby the sum of Type I and Type II is equal to 100 percent.

. When in such proportions and given a mild heat treatment a thermoset polymer is obtained sav ng agnelt; string and cure time as illustrated in'Table L' TABLE 1 Time required for certam esters to melt, string and cure Polyester of ethylene ycol and3',5cycloexadi'ene dicarboxyllc d,percent 1M 75 25 0 Polyester of ethylene glycol and maleic anhydridegpercant (TypeIlL'. 0 25 50 96? Timeto min. sec. min. sec. min. see. min. sec. min. sec.

' 35 0 2a 0 B (l 45 0 I 72 0 62 0 51 0 57 0 Nocure 126"-.. 0 18 0' 18 0 16 0 14 0 10 -12 0 14 0 16 0 19 0 70 33 0 21 0 2) 0 24 0 Nocure 150 0 10 0 10 0 8 0 8 0 l 6 13 0 7 0 ,7 0 7 0 Nocure mlymer may obtained as outlined in Examples 1 and2, respec' tively;

,EcampleL-A polymericester comprising the The data indicate that the curing time is signiilcantly shorter with a mixture of the two types of polymers than with either polymer alone.

reaction product of -ethylene glycol and transn3,5 o5 vFurthermore the curing time is appreciably reduced as the temperature is increased. The

linear polymers, alone, do not set in the absence of oxygen, under the conditions of these tests whereas the mixture thereof sets readily.

.The time necessary for a member of each type of polymer and for a 50/50 mixture of each melt, string or cure at C. in the absenceor presence of reducing and oxidizing agents or tbciit'ao' cc. r6

and oni a or. non-reducing surface is in'lable 2.

Trim 2 v l'flect various additives on stroke cure of polyesters at 125' C.

50/50 Mixture oi the polyesters oi ethyll00% Polyester oi ethylene glycol and one glycol and trans A3,5 cyclohexatrans A 3,6 cyclohexadiene dicarbdiene dicarboxylic acid-1,2 and the oxylic acid-1,2 pol esters oi ethylene glycol and m elc anhydride a Concen- Adam tration Time to- Time to Melt String Cure Melt smu Cure min. sec. min. sec. min. sec. min. sec. min. sec. min. sec.

0 l8 l2 0 33 0 0 l6 l6 0 20 0 d 0 25 i4 0 24 0 0 30 13 0 16 0 Lauroyl peroxid l. 0 0 20 5 0 24 0 0 13 ll 30 l5 15 D0. Cobalt naphthenate 1.0 0 15 0 29 0 0 13 ll 0 ill 0 Do..." Cuprons oxide 1.0 0 l4 l2 0 100 0 0 l2 2] 30 68 0 Do. White lead L0 0 13 i4 0 22 0 The data show that certain additives affect the melting, stringing and curing time of the polyester of ethylene glycol and the cyclohexadiene dicarboxylic acid. The oxidizing agent lauroyl peroxide reduces the stringing and curing time, cobalt naphthenate has a smaller effect, while the reducing agent cuprous oxide greatly lengthens the curingtime. The mixture containing equal proportions of the linear polymers. cures in less time on both a non-reducin and reducing surface (glass and steel) than does the polymer comprising the polyester of ethylene glycol and the cyclohexadiene dicarboxylic acid. The curing time of the polymer comprising the mixed esters is less in each case than is that of the polymer derived from the single ester. Here the oxidizing agent reduces the time necessary to eifect melting, stringing and curing, while the reducing agent cuprous oxide lengthens the time necessary to effect stringing and curing.

Although the invention has been illustrated by specific examples, it will become apparent to those skilled in the art that various modifications may be made in carrying out the process while retaining the benefit of the discoveries herein disclosed. For instance the specific examples relate to the reaction of ethylene glycol with the trans form of 133.5 cyclohexadiene dicarboxylic acid-1,2 in Type I polymer; however the cis form of 113,5 cyclohexadiene dicarboxylic acid- 1,2 may be used. The A35 acids are preferred since the A2,6 cyclohexadiene dicarboxylic acid: 1,2 requires higher reaction temperatures. Furthermore other dibasic alcohols, diamines or such as the following may be used:

condensation polymers and any linear compound or polymer containing at least two activated olefinic bonds. For example, alpha unsaturated acyclic dibasic carboxylic acids other than maleic acid such as fumaric, muconic or substituted muconic may be used and the activated olefinic groups may reside in either the dibasic acid portion of the polymer or the activated olefinic groups may reside in the bii'unctional alcohol or amine portion of the polymer or the activated olefinic groups may reside in a hydroxy acid or an amino acid linear polymer wherein the polymer is formed by the condensation of like molecules with each other; or the activated olefin groups may be present in a conjugated diene portion oi a polymeric product.

The examples disclose properties of the composition obtained in the reaction between the linear polymer A3,5 cyclohexadiene dicarboxylic acid-1,2 and ethylene glycol and a second linear polymer of maleic anhydride and ethylene glycol thermoset at temperatures of 100, and degrees centigrade. This composition and the other combinations with the A3,5 cyclohexadiene dicarboxylic acid disclosed herein thermoset in a relatively short period of time at temperatures of 70-90 C. However the curing is accelerated as the temperature is increased until at 200 C. the composition sets in less than six minutes. The A2,6 cyclohexadiene dicarboxylic acid, in the various combinations of compounds disclosed to form thermoset polymers, requires a somewhat higher temperature and longer time to effect curing than the A3,5 cyclohexadiene carboxylic acid and in some instances may require several hours.

Additionally, the invention embraces the reac- Monoglycerides may also be used.

tion of other proportions of the thermoplastic Furthermore in Type II polymers other dibasic 70 polymers than shown in the specific examples.

alcohols, diamines or amino alcohols as specified by Y earlier in the disclosure and as listed in the examples above may be used.

As previously stated the invention embraces thermosetting mixtures containing Type I linear 7s Measurable curing effects are obtained, for example, with as little as 1 percent of Type I polymer in Type II maleic acid polyesters or with as little as 1 percent of Type II polyesters in Type I polymer. Furthermore the reactions may be car- 7 ried out at other temperatures and time periods than those shown for purposes of illustration. Thus the reaction may be carried out at temperatures as low as about 70 C. if time is notof critical importance. Temperatures 'as high-as 200 C. are operative and require very shortthermopolymer molecule and iormed by the reaction of (c) an alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a member of the group consisting of the dihydric alcohols, the diamines and the amino-alcohols, the value oi "A" and 3" being such that the mathematical prodsetting times. Fnrexamplacuringof'mixtures oiTypeIandTypeIIpolymermaybeeflectedin as little as 0.01 hour at 150 C. Generally temperatures of from about 90 to.150 C. are most desirable, 100-135 C. being preferred. Furthermore, time and temperature necessary to eiiect curing are decreased by the presence of certain oxidizing agents as previously disclosed.

polymer formed by the reaction of (a) a cyclohexadiene dicarhoxylic acid having conjugated ethylenic unsaturation and (b) a member of the group consisting of the dihydric alcohols, the

not of (A-2) and (3-2) is atdeast about 10.

'7. A resinous composition comprising the condensation product of (I) a linear condensation polymer formed by the reaction of (a) a cyclohexadiene dicarboxylic acid having conjugated ethylenic unsaturation and (b) a member to! the'group consisting of the dihydric alcohols. the diamines and the amino-alcohols and (II) a linear condensation polymer formed by the reaction oi (c) an alpha, beta, ethylenically un-.

saturated aliphatic dicarboxylic acid and (d) a member of the group consisting oi the dihydric alcohols, the diamines and the amino-alcohols, the linear'condensation poiymerdesignated by the symbol (1) constituting from about 5% of about 95% of the total weight of the condensathe amino-alcohols and (II) a linear condensation polymer formed by the reactionof (c) an' alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a member of the group consisting of the dihydricalcohols, the diamines and the amino-alcohols.

2. A resinous composition comprising the condensation product of (I) a linear polyester formed by the reaction of ,(a) a cyclohexadiene dicarboulic acid having conjugated ethylenic unsaturation and (b) a dihydric alcohol and (11) a linear polyester formed by the reaction of (c) an alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a dihydric alcohol.

3. A resinous composition comprising the condensation product of (I) a linear polyester formed by the reaction of (a) A3,5-cyclohexadiene dicarboxylic-acid-lfland (b) a dihydric alcohol and (11) a linear polyester formed by the reaction of (c) an alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a dihydric alcohol. 1

4. A resinous composition comprising the condensation product of (I). a linear polyester formed by the reaction oi (a) Alli-cyclohexadiene dicarboxylic acid-1,2 and (b) a dihydric alcohol and (II) a linear polyester formed by the reaction of (c) an alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a dihydric alcohol. 1

5. A resinous composition comprising the condensation product of (I) the polyester of A3,5-

cyclohexadiene dicarboxylic acid-1,2 and ethylene glycol and (II) poly-ethylene-glycol-maleate.

6. A resinous composition comprising the condensation product of (I) a linear condensation polymer having an average of A cyclohexadiene radicals in the polymer molecule formed by the reaction of (u) a cyclohexadiene dicarboxvlic acid having conjugated ethylenic maturation and (b) a member of the group consisting of the dihydric alcohols. the diamines and the amino-alcohols and (11) a linear condensation polymer an average of B ethylenic groups in the tion reaction mixture from'which the resinous composition is obtained, the linear condensation polymer designated by the symbol (1!) constituting the balance of the weight of said condensation reaction mixture. V

8. A resinous composition comprising the condensation product of (I) a linear condensation polymer formed by the reaction of (a) acyclohexadiene dicarboxylic acid having conjugated ethylenic unsaturation and '(b) a member of the group consisting of the dihydric alcohols, the diamines and the amino-alcohols and (II) a linear condensation polymer formed by the reaction of (c) an alpha, beta, ethylenically unsaturated aliphatic dicarboxylic acid and (d) a member of the group consisting of the dihydric alco-' action mixture from which the resinous composition is obtained, the linear condensation polymer designated by the symbol (II) constituting the balance of the weight of said condensation reformed by the reaction of. (c) an alpha, beta, v

ethylenically unsaturated aliphatic dicarboxylic acid and (d) a member of the group consisting of the dihydic alcohols, the diamines and the amino-alcohols.

LUDWIG- H. DIMPFL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date.

2,323,706 D'AIEHO July 6, 1943 2,403,791 DAlelio July 9, 1946 

1. A RESINOUS COMPOSITION COMPRISING THE CONDENSATION PRODUCT OF (I) A LINEAR CONDENSATION POLYMER FORMED BY THE REACTION OF (A) A CYCLOHEXADIENE DICARBOXYLIC ACID HAVING CONJUGATED ETHYLENIC UNSATURATION AND (B) A MEMBER OF THE GROUP CONSISTING OF THE DIHYDRIC ALCOHOLS, THE DIAMINES AND THE AMINO-ALCOHOLS AND (II) A LINEAR CONDENSATION POLYMER FORMED BY THE REACTION OF (C) AN ALPHA, BETA, ETHYLENICALLY UNSATURATED ALIPHATIC DICARBOXYLIC ACID AND (D) A MEMBER OF THE GROUP CONSISTING OF THE DIHYDRIC ALCOHOLS, THE DIAMINES AND THE AMINO-ALCOHOLS. 